Patent GB-432628-A (GB)
Title: Improvements in or relating to the production of compounds containing an ethylenic linkage, or a polymethine chain
IPC: C09B23/10
Filed: 1933-12-23
Abstract: Compounds containing an ethylenic linkage or a polymethine chain are prepared by reacting an organic compound containing a ketomethylene (--COCH2--) group and which may be represented by one of the following general formul  <FORM:0432628/IV/1> or <FORM:0432628/IV/2> (wherein X stands for C, S or O), with a quaternary salt of a heterocyclic nitrogen compound containing as a reactive group an aryl-, alkyl-, or aralkyl-thioether or -selenoether, an aminovinyl, an arylaminovinyl, an acetaminovinyl, an acetarylaminovinyl or a halogen group.  Alternatively, the organic compound containing the ketomethylene grouping, the heterocyclic nitrogen base and an alkyl salt are mixed together and heated to effect quaternary salt formation simultaneously with the main condensation reaction.  Also such products are obtained by condensing with a heterocyclic quaternary ammonium salt having a reactive group, the condensation product of the compound containing the ketomethylene group and a formamidine or a formimino ether.  As starting materials the following ketomethylene compounds are mentioned: indanedione, a - and b -hydrindone, tetronic acid, a - and b -keto - dihydrothionaphthene, naphthathioindoxyls, ethoxythioindoxyls, a - and b -ketodihydrocoumarone; also for reaction therewith there may be used heterocyclic quaternary ammonium salts having thioether or selenoether groupings in a - or g -position or compounds formed by treating the corresponding N-alkyl thiones with alkyl salts (the selenoether derivatives are prepared by heating a - or g -chloro substituted heterocyclic nitrogen bases with alcoholic selenourea, followed by saponification and alkylation), and compounds formed by condensing formamidines or aryl-formamidines with quaternary salts of heterocyclic nitrogen bases having a reactive methyl group.  Many of the products are useful for mixing with photographic emulsions for modifying the light-sensitivity while others may be of use as textile dyes.  In examples, (1) 1,3-indanedione is condensed with diphenylformamidine in acetic anhydride and the product with 1-methylbenzthiazole ethyl - p - toluenesulphonate, lepidine methiodide and quinaldine ethiodide to give products which are represented as having a dimethenyl linkage, indanedione and heterocyclic radicles; (2) indanedione is condensed with 1-methylmercaptobenzthiazole ethiodide in pyridine to give N-ethyldihydrobenzthiazolyl-1<1>.2 - indane - 1.3 - dione; (3) 2 - hydrindone (derived from indene by bromination according to Walters's method, followed by treatment with alcoholic caustic potash and steam distillation from an acidified solution) is condensed with acetanilidovinylbenzthiazole ethiodide to give N - ethyldihydrobenzthiazolyl-1<1>.1-dimethenylindane-2-one; (4) 1-hydrindone is condensed with the product of 1-methylquinoline-2-thione and ethyl-p-toluenesulphonate to give N-methyldihydroquinolyl - 2.2<1> - indane - 1 -one.  Samples have been furnished under Sect. 2 (5) of products prepared as follows: (a) 1-methylmercaptobenzthiazole condensed with methyl-p-toluenesulphonate and the product further condensed with hydroxythiotolene (a -oxy-a <1>-methylthiophene); (b) b -courmaranone concondensed with 2-iodoquinoline ethiodide in presence of sodium ethoxide; (c) 2-methyl-selenomercaptoquinoline (prepared by reacting 2-chloroquinoline with selenourea (from cyanamide and hydrogen selenide) saponifying and methylating) is condensed with methyl-p-toluenesulphonate and then further heated with 1.3-indanedione to give N-methyldihydroquinolyl-2,2-indane-1,3-dione.